Single-phase lead-zirconate-titanate (PZT) perovskite nanofibers, with Pb(Zr0.5Ti0.5)O-3 composition were synthesized using the electrospinning technique. Poly-vinyl-pyrrolidone (PVP) was used as viscosity controller, size and uniformity of the Pb(Zr0.5Ti0.5)O-3 nanofibers were optimized against different PVP concentrations. The results showed that PVP concentrations play a significant role in the fabrication, homogeneity, uniformity, porosity, and particularly in the diameter of PZT nanofibers. SEM and XRD results revealed the formation of sing-phase Pb(Zr0.5Ti0.5)O-3 nanofibers at 600 degrees C with an average diameter of similar to 96 nm. The prepared PZT nanofibers exhibited a significantly wide bandgap (similar to 3.5 eV) and a high dielectric-constant (similar to 1827). The device of single-phase PZT nanofibers was fabricated on interdigitated electrodes to study the current-voltage, impedance spectroscopy, and dielectric characteristics of the PZT nanofibers. The current-voltage characteristics of the fabricated device with PZT nanofibers showed non-ohmic properties. The non-linear I-V characteristics at temperatures between 308 and 408 K indicate two distinct regions. Impedance spectroscopy indicated the presence of non-ideal Debye type behavior in Pb(Zr0.5Ti0.5)O-3 nanofibers and was ascribed to the existence of heterogeneity in the sample. The measured capacitances were assigned to two electro-active regions in the prepared Pb(Zr0.5Ti0.5)O-3 nanofibers. A proto-type piezoelectric nanogenerator based on PZT nanofibers was fabricated to study the piezoelectric properties of Pb(Zr0.5Ti0.5)O-3 nanofibers. PZT nanofibers were aligned on interdigitated electrodes of silver wire, which demonstrated piezoelectric performance and delivered an output voltage of similar to 40 V under periodic stress applications.